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Chemistry for Sustainable Development

2013 year, number 6

1.
Analyses of Mechanochemical Reactions at the Boundary between Metal Oxide Organic Fine Particles and Their Practical Application

M. SENNA
Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Yokohama 223-8522 (Japan)
E-mail: senna@applc.keio.ac.jp
Keywords: metal oxides, TiO2, PTFE, glycine, ligand exchange
Pages: 521527

Abstract >>
Starting from the colour change upon co-milling a white mixture comprising a metal oxide (MO) and organic solids (OS) with F or N, general features of the mechanochemical reactions at the boundaries between MO and OS were observed, characterized and discussed with the presence of various analytical results. Three parallel streams of the mechanochemical reactions upon co-milling are confirmed, i. e., i) an oxidative decomposition of the organic species, ii) formation of nanostructured carbon, and iii) incorporation of non-oxygen anionic species into oxides via a ligand exchange. In the case of wet milling, complex ion formation in a liquid phase is sandwiched. Case studies were focused on TiO2 as MO and polytetrafluoroethylene (PTFE) or glycine (Gly) as OS.



2.
Mechanochemical Synthesis in the Nutating Centrifugal Ball Mill

P. BILLIK1,2, M. GURTH2 and T. TURANYI3
1Faculty of Natural Sciences, Comenius University, Mlynska Dolina, SK-842 15 Bratislava (Slovakia)
E-mail: billik@fns.uniba.sk
2Institute of Measurement Science, Slovak Academy of Sciences, Dubravska cesta 9, 841 04 Bratislava (Slovakia)
3Kadaň Ltd., Lapaška cesta 458, 951 02 Pohranice (Slovakia)
Keywords: nutation, mechanochemical synthesis, TiO2, powders
Pages: 529533

Abstract >>
Mechanochemical synthesis of TiO2 by using the simple laboratory scale nutating centrifugal ball mill was demonstrated for the first time. In our prototype, the nutation angle in the range of 020 deg, besides the speed of rotation of central axes up to 1400 rpm, can be adjusted independently. In order to compare the milling efficiency between Nutator and high-energy planetary ball mill TB-2, the soft mechanochemical reaction between TiOSO4 ⋅ 2H2O and Na2CO3 has been studied. In the case of nutating mill the intensity of diffractions corresponding to TiOSO4 ⋅ 2H2O and Na2CO3 completely disappeared after 5 min milling. In case of the planetary ball mill TB-2, due to the large difference in the centrifugal forces (60g vs 20g), mechanochemical treatment for 1 min leads to similar results and after 10 min, the sample contains mainly rutile TiO2 with trace of TiO2-II.



3.
BIOMEC Process for Mechanochemical Biodegradation of Polycyclic Aromatic Hydrocarbons in Marine Sediments

G. CAGNETTA1, G. INTINI1, L. LIBERTI1, O. I. LOMOVSKY2 and V. V. BOLDYREV2
1Department of Civil, Environmental, Building Engineering and Chemistry, Technical University of Bari, 70123 Bari (Italy)
E-mail: g.cagnetta@gmail.com
2Institute of Solid State Chemistry and Mechanochemistry, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
Keywords: PAHs, marine sediment, mechanochemical treatment, biological treatment
Pages: 535543

Abstract >>

BIOMEC, a new two-stage process based on a short mechanochemical (MC) pre-treatment followed by biological treatment with purposely selected bacteria (Novosphingobium pentaromativorans), was investigated to detoxify Tarantos harbour (S. Italy) marine sediments contaminated by polycyclic aromatic hydrocarbons (PAHs) and classified as hazardous waste, according the Italian law (Legislative Decree 152/2006). The experimental results, aimed at determining the overall efficiency of the BIOMEC treatment, indicated that PAHs degradation may be achieved in a very effective (97 %) and fast (<14 days) manner, yielding a non-toxic waste largely reusable as building material. In particular the MC pre-treatment allowed bigger degradation of high MW PAHs; because of their larger aromatic structure, after collisions between sediment particles and milling bodies these congeners may generate more stable free radicals with respect to low MW ones and the probability of their formation is higher, hence they are MC degraded to larger extent. GC-MS analysis of MC degradation products of benzo(a)pyrene (BaP), spiked on clean sediment (taken from Tarantos harbour too), suggest that the first probable step is an almost complete destruction of BaP rings and the formation of oxidized heavy molecules with residual aromaticity. Then the breakdown of this kind of compounds and the formation of small radicals give origin to many volatile organic molecules which, through an accretion process, form heavier compounds up to graphitization.



4.
Microstructure of Cold Rolled Magnesium and Magnesium Hydrides for Hydrogen Storage Applications

J. LANG1, N. SKRYABINA2, D. FRUCHART3, M. DANAIE4 and J. HUOT1
1Chemistry and Physics Department, Universit du Qubec Trois-Rivires, 3351 des Forges, Trois-Rivires, Qubec, G9A 5H7 (Canada)
2Department of Physics, Perm State University, Ul. Bukireva 15, Perm 614990 (Russia)
3Institut Nel BP 166, 38042 Grenoble Cedex 9 (France)
4Department of Materials Science and Engineering, McMaster University, Hamilton, Ontario (Canada)
Keywords: hydrogen absorbing materials, magnesium alloys, cold rolling, gas-solid reactions
Pages: 545552

Abstract >>

It has recently been shown that Severe Plastic Deformation (SPD), and particularly cold rolling, techniques could be used to obtain nanostructured metal hydrides with enhanced hydrogen sorption properties. Cold rolling is a particularly interesting technique because it is easily scalable to industrial level. We present here the effect of cold rolling on hydrogen storage properties of magnesium and magnesium hydride (MgH2). Commercial magnesium and magnesium hydride were processed in a vertical cold rolling apparatus. For pure magnesium, a highly textured material was obtained after only one roll and first hydrogenation was faster than unprocessed magnesium. In the case of magnesium hydride, after only five rolling passes hydrogen sorption kinetics at 623 K were greatly enhanced without noticeable loss of capacity. The improvement in sorption kinetics is attributed due to the nanocrystalline structure and number of created defects. Investigation of the powder morphology and crystal structure indicates that cold rolling is equivalent to ball milling.



5.
Twinning Mechanism of Solid-State Reactions

M. SH. AKCHURIN, R. M. ZAKALYUKIN and A. A. KAMINSKY
Shubnikov Institute of Crystallography, Russian Academy of Sciences, Leninsky Pr. 59, Moscow 119333 (Russia)
E-mail: akchurin@ns.crys.ras.ru
Keywords: plastic deformation, twinning, mechanosynthesis, solid-state reactions
Pages: 553559

Abstract >>
A new mechanism of solid-state reactions, based on a mass transfer process due to the plastic deformation is proposed. By the example of the nucleation in the course of the mechanosynthesis of complex oxides, there has been demonstrated a role of twinning processes in the nucleation of spinel (MgAl2O4), lead titanate (PbTiO3) and yttrium-aluminum garnet (Y3Al5O12) under grinding the powders of MgO + Al2O3, TiO2 + PbO and Al2O3 + Y2O3, respectively. It has been proposed that the mechanical twinning is the main mechanism of mechanochemical solid-state reactions.



6.
Mechanochemical Sense of the Technology of Chemical Mechanical Polishing of Materials

A. S. ARTEMOV
Prokhorov Institute of General Physics, Russian Academy of Sciences, Ul. Vavilova, 38, Moscow 119991 (Russia)
E-mail: artpoliofan@mail.ru
Keywords: chemical and mechanical polishing, amorphous SiO2 particles, polishers, single crystals, mechanochemical activation
Pages: 561568

Abstract >>
Interpretation of the mechanochemical aspect from the viewpoint of the manifestation of P. A. Rebin-der effect is proposed on the basis of the experimental investigation of the kinetics and mechanism of the processes taking place during chemical mechanical polishing semiconductors, dielectric and metal crystals. The possibility of the tribochemical activation of chemical reactions by the flow of liquid silica sols under the joint action of chemical mechanical factors on the surface is demonstrated. It is established that solid particles promote activation and localization of chemical reactions on the surface of crystals on the atomic scale, and removal of the products of chemical reactions in the nanoscale. As a result, a mirror-smooth surface with subnanosecond relief is formed; containing no micro and nano scratches, pits, etched regions and other microdefects.



7.
Effect of Mechanical Activation on the Synthesis of Lead Ferroniobate

A. A. GUSEV1, I. P. RAEVSKY2, E. G. AVVAKUMOV1 and V. P. ISUPOV1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: gusev@solid.nsc.ru
2Research Institute of Physics, Southern Federal University,
Pr. Stachki 194, Rostov-na-Donu 344090 (Russia)
E-mail: igorraevsky@gmail.com
Keywords: lead ferroniobate, thermal synthesis from iron, niobium and lead oxides using mechanical activation
Pages: 569575

Abstract >>
The synthesis of lead ferroniobate from lead, iron and niobium oxides taken in the stoichiometric ratio was investigated for the purpose of choosing the optimal compositions, conditions of mechanical activation and subsequent thermal treatment. The process was carried out in the presence of the excess of lead oxide to prevent the deviation from the stoichiometry of the ceramics obtained after sintering. The changes of the phase composition of mixtures during mechanical activation and subsequent thermal treatment were followed. It was demonstrated that the most attractive structure and properties are those characterizing lead niobate obtained with some excess of lead oxide over the stoichiometric composition. It was established that with the help of mechanical activation it is possible to vary within a broad range the temperature of the magnetic phase transition for the powders and ceramics of lead ferroniobate.



8.
Solid-Phase Copolymerization of L,D-lactide with Chitosan

T. S. DEMINA1, L. V. VLADIMIROV2, T. A. AKOPOVA1 and A. N. ZELENETSKY1
1Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences, Ul. Profsoyuznaya 79, Moscow 117393 (Russia)
E-mail: detans@gmail.com
2Semenov Institutes of Chemical Physics, Russian Academy of Sciences, Ul. Kosygina 4, Moscow 119991(Russia)
Keywords: solid-phase synthesis, chitosan, lactide, grafted copolymers, biocompatible materials
Pages: 577583

Abstract >>
With the use of solid-phase synthesis in an extruder, chitosan and L,D-lactide grafted copolymers were obtained. A mechanism of graft polymerization was proposed, an effect of process conditions exerted on the yield and structure of the target products was studied. Based on the data obtained from fractionation, IR spectroscopy and study of the elemental composition of the fractions, a substitution level has been calculated for the chitosan amino groups that were 0.190.41. An average polymerization level for lactide in grafted chains and an effect exerted by the grafting on the solubility of chitosan and physico mechanical characteristics of film materials were determined. Based on the copolymers synthesized, three-dimensional matrices have been obtained for tissue engineering (macroporous hydrogels, spherical microparticles), as well as compatibility and biodegradation rate have been estimated for the materials.



9.
Mechanosynthesis of CuFe3C Nanocomposites Using Liquid Hydrocarbon

M. A. EREMINA, S. F. LOMAEVA, E. P. ELSUKOV, A. L. ULYANOV and A. A. CHULKINA
Physical-Technical Institute, Ural Branch of the Russian Academy of Sciences, Ul. Kirova 132, Izhevsk 426000 (Russia)
E-mail: mrere@mail.ru
Keywords: mechanical alloying, nanocomposites, copper, cementite
Pages: 585592

Abstract >>
Features of the formation of macro and microstructural state and the phase composition of Cu30 vol. % Fe3C nanocomposites obtained by mechanical alloying of copper and iron powders in the liquid source of carbon (xylene) followed by thermal treatment were studied by means of X-ray phase analysis, Mssbauer spectroscopy, scanning electron and optical microscopy, measurement of dynamic magnetic susceptibility. It was demonstrated that iron carbides are not formed during alloying; however, for the alloys obtained by grinding for 96 h, annealing at a temperature above 500 leads to the formation of cementite with the volume fraction of about 30 %. The grain size of the copper matrix of this composite is 10 nm, while after annealing at 800 it is 30 nm.



10.
Geopolymers based on mechanically activated Non-Ferrous Slags

A. M. KALINKIN1, T. C. ALEX2, S. K. NATH2, B. I. GUREVICH1, E. V. KALINKINA1, V. V. TYUKAVKINA1 and SANJAY KUMAR2
1Tananaev Institute of Chemistry and Technology of Rare Elements and Mineral Raw Materials, Kola Science Centre of the Russian Academy of Sciences, Ul. Fersmana 26A, Murmansk Region, Apatity 184209 (Russia)
E-mail: kalinkin@chemy.kolasc.net.ru
2CSIR-National Metallurgical Laboratory, Jamshedpur 831007 (India)
Keywords: Zn slag, CuNi slag, geopolymerisation, mechanical activation, carbon dioxide, reactivity, compressive strength
Pages: 593601

Abstract >>
Geopolymerisation behaviour of Imperial Smelting Furnace (ISF) Zn slag and granulated CuNi slag, mechanically activated in air and in CO2 atmosphere (P = 105 Pa) has been studied by XRD, SEM, FTIR, and isothermal conduction calorimetry. Mechanical activation of the slags has been carried out in a centrifugal-planetary mill AGO-2. Geopolymer samples have been prepared by mixing of the mechanically activated slag powders with NaOH solution or liquid glass and curing at (202) oC for up to 180 days. It has been observed that the ISF Zn slag and the granulated CuNi slag are suitable for the synthesis of building materials through geopolymerisation. The effect of milling atmosphere on properties of geopolymers is found to be alkaline reagent specific. A suitable combination of the milling atmosphere and alkaline reagent is required to realize the beneficial effect on mechanical properties of the geopolymer.



11.
Features of the Crystallization of Aluminohydroxide Gel Containing Mechanochemically Prepared Nanosized α-Al2O3 Particles

G. R. KARAGEDOV1, S. S. KOSOLOBOV2, A. V. LATYSHEV2, N. Z. LYAKHOV1 and A. L. MYZ1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: garik@solid.nsc.ru
2Rzhanov Institute of Semiconductor Physics, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 13, Novosibirsk 630090 (Russia)
Keywords: aluminium oxide, nanopowder, synthesis, mechanochemistry
Pages: 603608

Abstract >>
The introduction of α-Al2O3 nanoparticles into the gel formed during the hydrolysis of aluminium nitrate causes a substantial decrease in the temperature of its transition tino thermodynamically stable modification. The higher is the concentration of seeding within the range 0.25 mass %, the lower is the temperature of the formation of monophase α-Al2O3. At the sme time, the temperature of phase transition into the α-modification depends on the method of introduction of the seeding into the gel. This may be connected with nonuniform distribution of nanoparticles over its volume. The use of deionized water as a solvent instead of distilled water allows decreasing the temperature of α-Al2O3 formation to 500 C. Due to the low temperature of the formation of a-phase (<950 C), the product consists of easily destroyable granules formed by nanoparticles 4560 nm in size. Nevertheless, the samples formed from powders with close size demonstrate different sintering ability during low-temperature annealing in the air (1300 C). Their densities vary within the range 6797 % of the theoretically possible value. This is likely to be connected with the fact that separate particles in granules get grown together under unfavourable conditions.



12.
Mechanochemical Preparation of the Composites of Betulin Esters with Arabinogalactan and Investigation of Their Physicochemical Properties

S. A. KUZNETSOVA1,2, YU. N. MALYAR1, T. P. SHAKHTSHNEIDER3,4, M. A. MIKHAILENKO3, V. A. DREBUSCHAK4,5 and V. V. BOLDYREV3,4
1Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences, Ul. K. Marksa 42, Krasnoyarsk 660049 (Russia)
E-mail: ksa@icct.ru
2Siberian Federal University, Pr. Svobodny 79, Krasnoyarsk 664041 (Russia)
3Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
4Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russia)
5Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Koptyuga 3, Novosibirsk 630090 (Russia)
Keywords: betulin diacetate, betulin dipropionate, arabinogalactan, mechanochemical treatment, dissolution, gel-permeation chromatography
Pages: 609614

Abstract >>
Mechanically activated composites of betulin diacetate and dipropionate with water-soluble natural polysaccharide arabinogalactan were obtained. It was established that the composites are characterized by increased concentration of betulin diacyls during their dissolution in water. The formation of molecular complexes of betulin diacetate and dipropionate with arabinogalactan during mechanical activation and during the dissolution of initial and mechanically activated mixtures in water was assumed. The complexes of betulin diacyls with arabinogalactan were also obtained in the form of thin films, readily soluble in water.



13.
Influence of Mechanical Activation Conditions upon the Physicochemical Properties of Manganese-Substituted Cordierite Ceramics

E. F. SUTORMINA,L. A. ISUPOVA,A. A. MARCHUK,A. V. KUZNETSOVA andV. A. ROGOV
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
E-mail: selena@catalysis.ru
Keywords: substituted cordierite, mechanical activation, ammonia oxidation
Pages: 615620

Abstract >>
An effect of different mechanical activation conditions (different activator types) on the phase composition, texture characteristics of catalysts based on manganese-substituted cordierite ceramics, as well as the activity thereof in the reaction of ammonia oxidation was studied. It is demonstrated that it is preferable to use an energy-intensive planetary ball mill with a high power density, since it provides the preparation of smaller particles. The finely crystallized manganese cordierite with a minor impurities content, low specific surface, low pore volume and a high activity in the reaction of ammonia oxidation is obtained at their subsequent sintering.



14.
Nanosized Magnetic Powder on the Ground of Oxides in Medicine and Biology

O. G. TEREKHOVA1, A. A. MAGAEVA1 and E. P. NAIDEN1,2
1Department of Structural Macrokinetics, Tomsk Scientific Centre, Siberia Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 10/4, Tomsk 634021 (Russia)
E-mail: terog@dsm.tsc.ru
2Tomsk State University, Pr. Lenina 36, Tomsk 634050 (Russia)
Keywords: oxide nanoferrimagnetics, mechanochemical synthesis, adsorption onto nanoparticles, magnetofection
Pages: 621628

Abstract >>
A method is presented for producing nanosized oxide ferromagnetics from salt systems with the use of the mechanochemical activation and their fundamental properties are investigated. Results concerning the use of the oxide ferrimagnetics synthesized for the magnetofection of DNA, DNA/RNA sorption, microbial cells, proteins, and contrast agents for MRT diagnostics are reported. It has been found that nanoparticles are non-toxic; their distribution in internal organs and the decrease dynamics, the possibility of using them for medication transport have been demonstrated.



15.
Using the Mechanical Activation for Obtaining the Sulphide Catalysts of Hydrogenolysis

T. A. FEDUSCHAK1, M. A. UYMIN2, A. E. ERMAKOV2, A. S. AKIMOV1, N. N. SCHEGOLEVA2, T. V. PETRENKO1, S. P. ZHURAVKOV3 and A. V. VOSMERIKOV1
1Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
E-mail: taina@ipc.tsc.ru
2Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ul. S. Kovalevskoy 18, Yekaterinburg 620990 (Russia)
3Tomsk Polytechnic University, Pr. Lenina 30, Tomsk 634050 (Russia)
Keywords: mechanical activation, hydrorefining, sulphide catalysts, model reaction, hydrodesulphurisation of dibenzothiophene
Pages: 629633

Abstract >>
For the first time, an approach to a single-stage manufacture of bulky sulphide catalysts using a solid-phase method performed by means of the mechanical activation of a mixture consisting of coarse molybdenum disulphide and cobalt powders, in the presence of detonation nanodiamonds is described. An effect exerted by the mechanical treatment duration, ratio between the initial components and nanodiamonds on the process of nanofragmentation of molybdenum disulphide and activity of catalytic systems obtained in the model reaction of DBT hydrodesulphurisation has been studied.